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Estimating relative disulfide energies : an accurate ab initio potential energy surface

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journal contribution
posted on 2010-01-01, 00:00 authored by N Haworth, J Liu, S Fan, J Gready, Merridee Wouters
Disulfide torsional energy, a good predictor of disulfide redox potential in proteins, may be estimated by interpolation on a potential energy surface (PES) describing the twisting of diethyl disulfide through its three central dihedral angles. Here we update PES calculations at the M05-2X level of theory with the 6-31G(d) basis set. Although the surface shows no qualitative differences from an earlier MP2(full) PES, energy differences greater than 1 kJ mol–1 were seen for conformations with χ2 between –60° and 30°, or with χ3 below 60° or above 130°. This is particularly significant for highly strained disulfides that are likely to be spontaneously reduced by mechanical means. In benchmarking against the high-level G3X method, M05-2X showed significantly reduced root mean squared deviation compared with MP2(full) (1.0 versus 2.0 kJ mol–1 respectively). Results are incorporated into a web application that calculates relative torsional energies from disulfide dihedral angles (http://www.sbinf.org/applications/pes.html).

History

Journal

Australian journal of chemistry

Volume

63

Issue

3

Pagination

379 - 387

Publisher

CSIRO

Location

Melbourne, Vic.

ISSN

0004-9425

eISSN

1445-0038

Language

eng

Publication classification

C1.1 Refereed article in a scholarly journal; C Journal article

Copyright notice

2010, CSIRO

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